JP2021512179A - A cross-linking agent compound, a photosensitive composition containing the same, and a photosensitive material using the same. - Google Patents
A cross-linking agent compound, a photosensitive composition containing the same, and a photosensitive material using the same. Download PDFInfo
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- JP2021512179A JP2021512179A JP2020528337A JP2020528337A JP2021512179A JP 2021512179 A JP2021512179 A JP 2021512179A JP 2020528337 A JP2020528337 A JP 2020528337A JP 2020528337 A JP2020528337 A JP 2020528337A JP 2021512179 A JP2021512179 A JP 2021512179A
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- linking agent
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Links
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical group C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000006836 terphenylene group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
本発明は、末端架橋性官能基がシラン系保護基でキャップされた架橋剤化合物、これを含む感光性組成物、およびこれを利用した感光材料に関する。The present invention relates to a cross-linking agent compound in which a terminal cross-linking functional group is capped with a silane-based protecting group, a photosensitive composition containing the same, and a photosensitive material using the same.
Description
[関連出願の相互参照]
本出願は、2018年12月21日付の韓国特許出願第10−2018−0167760号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
[Cross-reference of related applications]
This application claims the benefit of priority under Korean Patent Application No. 10-2018-0167760 dated December 21, 2018, and all the contents disclosed in the literature of the Korean patent application are part of this specification. Included as a part.
本発明は、架橋性に優れ、溶媒に対する溶解性が向上した架橋剤化合物、感光材料合成時に優れた機械的強度および貯蔵安定性を実現できる感光性組成物、およびこれを利用した感光材料に関する。 The present invention relates to a cross-linking agent compound having excellent cross-linking property and improved solubility in a solvent, a photosensitive composition capable of realizing excellent mechanical strength and storage stability during synthesis of a photosensitive material, and a photosensitive material using the same.
感光性樹脂は、各種精密電子・情報産業製品の生産に実用化された代表的な機能性高分子材料であって、現在、先端技術産業、特に半導体およびディスプレイの生産に重要に用いられている。 The photosensitive resin is a typical functional polymer material that has been put into practical use in the production of various precision electronic and information industry products, and is currently importantly used in the advanced technology industry, especially in the production of semiconductors and displays. ..
一般に、感光性樹脂は、光照射によって短時間で分子構造の化学的変化が起こり、特定の溶媒に対する溶解度、着色、硬化などの物性変化が起こる高分子化合物を意味する。感光性樹脂を利用すれば微細精密加工が可能であり、熱反応工程に比べてエネルギーおよび原料を大きく節減することができ、小さい設置空間で迅速かつ正確に作業を行うことができ、先端の印刷分野、半導体生産、ディスプレイ生産、光硬化表面コーティング材料などの各種精密電子・情報産業分野で多様に使用されている。 In general, a photosensitive resin means a polymer compound in which a chemical change in molecular structure occurs in a short time by light irradiation, and physical properties such as solubility, coloring, and curing in a specific solvent change. Fine precision processing is possible by using photosensitive resin, energy and raw materials can be greatly reduced compared to the thermal reaction process, work can be performed quickly and accurately in a small installation space, and tip printing. It is widely used in various precision electronics and information industries such as fields, semiconductor production, display production, and photo-curing surface coating materials.
一方、最近、電子機器が高集積化および微細パターン化されながら、不良率を極小化することができ、処理効率と解像度を高めることができる感光性樹脂が要求されている。これにより、ポリアミド酸またはポリアミック酸などを感光性樹脂として使用する方法が紹介されている。 On the other hand, recently, there is a demand for a photosensitive resin capable of minimizing the defect rate and increasing the processing efficiency and the resolution while the electronic device is highly integrated and finely patterned. This introduces a method of using a polyamic acid, a polyamic acid, or the like as a photosensitive resin.
しかし、ポリアミド酸は、空気中の水分などにより容易に加水分解されて保存性および安定性が十分ではなく、ポリアミック酸は、適用される基板などに対する密着性が低く、高温の適用により電気配線や基板の物性を低下させるという問題があった。特に、感光性樹脂は、最終的に硬化した状態での機械的物性が十分でないという問題があった。 However, polyamic acid is easily hydrolyzed by moisture in the air and has insufficient storage stability and stability, and polyamic acid has low adhesion to the substrate to which it is applied. There was a problem of deteriorating the physical properties of the substrate. In particular, the photosensitive resin has a problem that the mechanical properties in the finally cured state are not sufficient.
それで、ディスプレイ分野で要求される高い機械的物性を有する感光材料を製造するために、多様な架橋剤を感光性組成物に添加する方案が提案されたが、架橋剤化合物の溶解性が十分ではなく、安定性および分散性が低下して、感光性組成物が均一性を有することができず、信頼性が低下する限界があった。 Therefore, in order to produce a photosensitive material having high mechanical properties required in the display field, a method of adding various cross-linking agents to the photosensitive composition has been proposed, but the solubility of the cross-linking agent compound is not sufficient. There was a limit to the decrease in stability and dispersibility, the inability of the photosensitive composition to have uniformity, and the decrease in reliability.
したがって、架橋性に優れて優れた機械的物性を実現でき、かつ、溶解性が向上して組成物内で優れた貯蔵安定性および分散性を有することができる架橋剤化合物の開発が要求されている。 Therefore, it is required to develop a cross-linking agent compound which is excellent in cross-linking property and can realize excellent mechanical properties, and can have improved solubility and excellent storage stability and dispersibility in the composition. There is.
本発明は、架橋性に優れ、溶媒に対する溶解性が向上した架橋剤化合物を提供するものである。 The present invention provides a cross-linking agent compound having excellent cross-linking property and improved solubility in a solvent.
また、本発明は、感光材料合成時に優れた機械的強度および貯蔵安定性を実現できる感光性組成物を提供するものである。 The present invention also provides a photosensitive composition capable of achieving excellent mechanical strength and storage stability during the synthesis of photosensitive materials.
また、本発明は、前記感光性組成物を利用した感光材料を提供するものである。 The present invention also provides a photosensitive material using the photosensitive composition.
本発明は、下記化学式1で表される架橋剤化合物が提供される。
[化学式1]
[Chemical formula 1]
また、本発明は、前記架橋剤化合物を含む感光性組成物が提供される。 The present invention also provides a photosensitive composition containing the cross-linking agent compound.
また、本発明は、前記架橋剤化合物および少なくとも1つ以上のカルボキシル基を含む高分子を含む感光性組成物が提供される。 The present invention also provides a photosensitive composition containing the cross-linking agent compound and a polymer containing at least one or more carboxyl groups.
また、本発明は、前記感光性組成物の硬化物を含む、感光材料が提供される。 The present invention also provides a photosensitive material containing a cured product of the photosensitive composition.
以下、本発明の具体的な実施形態による架橋剤化合物、これを含む感光性組成物、およびこれを利用した感光材料についてより詳細に説明する。 Hereinafter, a cross-linking agent compound according to a specific embodiment of the present invention, a photosensitive composition containing the same, and a photosensitive material using the same will be described in more detail.
本明細書において特別な制限がない限り、次の用語は以下の通り定義される。 Unless otherwise specified herein, the following terms are defined as follows:
本明細書において、ある部分がある構成要素を'含む'とすると、これは、特に反対する記載がない限り、他の構成要素を除外するのではなく、他の構成要素をさらに含むことができることを意味する。 As used herein, if a component is'included'in a component, it may include other components further, rather than excluding other components, unless otherwise stated otherwise. Means.
本明細書において、'置換'という用語は、化合物内の水素原子の代わりに他の官能基が結合することを意味し、置換される位置は水素原子が置換される位置、つまり、置換基が置換可能な位置であれば限定されず、2以上置換される場合、2以上の置換基は互いに同一または異なっていてもよい。 As used herein, the term'substitution'means that another functional group is attached in place of the hydrogen atom in the compound, and the position to be substituted is the position where the hydrogen atom is substituted, that is, the substituent is. The position is not limited as long as it can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.
本明細書において、'置換または非置換の'という用語は、重水素;ハロゲン基;シアノ基;ニトロ基;ヒドロキシ基;カルボニル基;エステル基;イミド基;アミド基;アミノ基;カルボキシ基;スルホン酸基;スルホンアミド基;ホスフィンオキシド基;アルコキシ基;アリールオキシ基;アルキルチオキシ基;アリールチオキシ基;アルキルスルホキシ基;アリールスルホキシ基;シリル基;ホウ素基;アルキル基;シクロアルキル基;アルケニル基;アリール基;アラルキル基;アラルケニル基;アルキルアリール基;アリールホスフィン基;またはN、O、およびS原子のうちの1個以上を含むヘテロ環基からなる群から選択される1個以上の置換基で置換または非置換されるか、前記例示された置換基のうちの2以上の置換基が連結された置換または非置換されたものを意味する。例えば、'2以上の置換基が連結された置換基'は、ビフェニル基であってもよい。すなわち、ビフェニル基は、アリール基であってもよく、2個のフェニル基が連結された置換基と解釈されてもよい。 As used herein, the term'substituted or unsubstituted' refers to heavy hydrogen; halogen group; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amide group; amino group; carboxy group; sulfone. Acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkylthioxy group; arylthioxy group; alkylsulfoxi group; arylsulfoxi group; silyl group; boron group; alkyl group; cycloalkyl group; Alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; arylphosphin group; or one or more selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms. It means substituted or unsubstituted with a substituent, or substituted or unsubstituted in which two or more substituents among the above-exemplified substituents are linked. For example, the'substituent in which two or more substituents are linked'may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are linked.
本明細書において、(共)重合体は、重合体または共重合体を全て含む意味であり、前記重合体は、単一の繰り返し単位からなる単独重合体を意味し、共重合体は、2種以上の繰り返し単位を含む複合重合体を意味する。 In the present specification, the (co) polymer means a polymer or a copolymer including all of them, the polymer means a homopolymer composed of a single repeating unit, and the copolymer means 2 It means a copolymer containing a repeating unit of more than one species.
本明細書において、(共)重合体は、ランダム(共)重合体、ブロック(共)重合体、グラフト(共)重合体などを全て含む意味で使用される。 In the present specification, the (co) polymer is used in the sense of including all random (co) polymers, block (co) polymers, graft (co) polymers and the like.
本明細書において、
本明細書において、アルキル基は直鎖または分枝鎖であり、炭素数は特に限定されないが、1〜10であることが好ましい。他の実施形態によれば、前記アルキル基の炭素数は1〜6である。アルキル基の具体的な例としては、メチル、エチル、プロピル、n−プロピル、イソプロピル、ブチル、n−ブチル、イソブチル、tert−ブチル、sec−ブチル、1−メチル−ブチル、1−エチル−ブチル、ペンチル、n−ペンチル、イソペンチル、ネオペンチル、tert−ペンチル、ヘキシル、n−ヘキシル、1−メチルペンチル、2−メチルペンチル、4−メチル−2−ペンチル、3,3−ジメチルブチル、2−エチルブチル、ヘプチル、n−ヘプチル、1−メチルヘキシル、シクロペンチルメチル、シクロヘプチルメチル、オクチル、n−オクチル、tert−オクチル、1−メチルヘプチル、2−エチルヘキシル、2−プロピルペンチル、n−ノニル、2,2−ジメチルヘプチル、1−エチル−プロピル、1,1−ジメチル−プロピル、イソヘキシル、2−メチルペンチル、4−メチルヘキシル、5−メチルヘキシルなどがあるが、これらに限定されない。 In the present specification, the alkyl group is a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. According to other embodiments, the alkyl group has 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, Pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , N-Heptyl, 1-methylhexyl, Cyclopentylmethyl, Cycloheptylmethyl, Octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.
本明細書において、アルキレン基は、アルカン(alkane)に由来する2価の官能基であって、炭素数は1〜20、または1〜10、または1〜5である。例えば、直鎖型、分枝型または環状であり、メチレン基、エチレン基、プロピレン基、イソブチレン基、sec−ブチレン基、tert−ブチレン基、ペンチレン基、へキシレン基などになることができる。前記アルキレン基に含まれている一つ以上の水素原子は、それぞれ前記アルキル基の場合と同様の置換基に置換可能である。 As used herein, the alkylene group is a divalent functional group derived from an alkane and has 1 to 20, or 1 to 10, or 1 to 5 carbon atoms. For example, it is linear, branched or cyclic and can be a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group or the like. One or more hydrogen atoms contained in the alkylene group can be substituted with the same substituents as in the case of the alkyl group.
本明細書において、アリール基は、アレーン(arene)に由来する1価の官能基であって、特に限定されないが、炭素数6〜20であることが好ましく、単環式アリール基または多環式アリール基であってもよい。前記単環式アリール基としては、フェニル基、ビフェニル基、ターフェニル基などになってもよいが、これらに限定されるものではない。前記多環式アリール基としては、ナフチル基、アントラセニル基、フェナントリル基、ピレニル基、ペリレニル基、クリセニル基、フルオレニル基などになってもよいが、これらに限定されるものではない。前記アリール基は、置換または非置換されていてもよい。 In the present specification, the aryl group is a monovalent functional group derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and is a monocyclic aryl group or a polycyclic group. It may be an aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto. The polycyclic aryl group may be, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a peryleneyl group, a chrysenyl group, a fluorenyl group and the like. The aryl group may be substituted or unsubstituted.
本明細書において、アリーレン基は、アレーン(arene)に由来する2価の官能基であって、単環式または多環式であってもよく、炭素数は6〜20、または6〜10である。例えば、フェニレン基、ビフェニレン基、ターフェニレン基、スチルベニレン基、ナフチレニル基などになってもよいが、これらに限定されるものではない。前記アリーレン基に含まれている一つ以上の水素原子は、それぞれ前記アルキル基の場合と同様の置換基に置換可能である。 In the present specification, the arylene group is a divalent functional group derived from arene, which may be monocyclic or polycyclic, and has 6 to 20 or 6 to 10 carbon atoms. is there. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a stillbenylene group, a naphthylenel group, or the like, but is not limited thereto. One or more hydrogen atoms contained in the arylene group can be substituted with the same substituents as in the case of the alkyl group.
本明細書において、多価官能基は、任意の化合物に結合した複数の水素原子が除去された形態の残基であって、例えば、2価の官能基、3価の官能基、4価の官能基が挙げられる。一例として、シクロブタンに由来する4価の官能基は、シクロブタンに結合した任意の水素原子4つが除去された形態の残基を意味する。 As used herein, a polyvalent functional group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound have been removed, and is, for example, a divalent functional group, a trivalent functional group, or a tetravalent functional group. Functional groups can be mentioned. As an example, a tetravalent functional group derived from cyclobutane means a residue in the form in which any four hydrogen atoms attached to cyclobutane have been removed.
本明細書において、直接結合または単一結合は、当該位置にいかなる原子または原子団も存在せず、結合線で連結されることを意味する。具体的には、化学式中、RaまたはLb(aおよびbは、それぞれ1〜20の整数)で表示される部分に他の原子が存在しないことを意味する。 As used herein, a direct bond or a single bond means that no atom or group of atoms is present at that position and is connected by a bond line. Specifically, it means that no other atom exists in the portion represented by Ra or L b (a and b are integers of 1 to 20, respectively) in the chemical formula.
本明細書において、重量平均分子量は、GPC法によって測定したポリスチレン換算の重量平均分子量を意味する。前記GPC法によって測定したポリスチレン換算の重量平均分子量を測定する過程では、通常公知の分析装置と示差屈折率検出器(Refractive Index Detector)などの検出器および分析用カラムを用いることができ、通常適用される温度条件、溶媒、flow rateを適用することができる。前記測定条件の具体的な例としては、Polymer Laboratories PLgel MIX−B 300mm長さのカラムを用い、Waters PL−GPC220機器を用いて、評価温度は160℃であり、1,2,4−トリクロロベンゼンを溶媒として使用し、流速は1mL/minの速度で、サンプルは10mg/10mLの濃度に調製した後、200μLの量で供給し、ポリスチレン標準を用いて形成された検量線を用いてMw値を求めることができる。ポリスチレン標準品の分子量は、2,000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000の9種を使用した。 In the present specification, the weight average molecular weight means the polystyrene-equivalent weight average molecular weight measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzer, a detector such as a differential refractive index detector, and a column for analysis can be used, and are usually applied. The temperature conditions, solvent, and flow rate to be applied can be applied. As a specific example of the measurement conditions, a Polystyrene Laboratories PLgel MIX-B 300 mm long column is used, a Waters PL-GPC220 instrument is used, the evaluation temperature is 160 ° C., and 1,2,4-trichlorobenzene is used. Was used as a solvent, the flow rate was 1 mL / min, the sample was prepared to a concentration of 10 mg / 10 mL, then supplied in an amount of 200 μL, and the Mw value was determined using a calibration curve formed using a polystyrene standard. Can be sought. The molecular weight of polystyrene standard products is 9 of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000. Seeds were used.
本発明者らは、本発明に係る架橋剤化合物が上記化学式1で表されるように、架橋性官能基であるヒドロキシ基(−OH)の末端をR1およびR2の特定の官能基に置換する場合、R1およびR2の官能基が保護基として作用して、架橋剤化合物の溶解性および分散性が高くなり、架橋剤化合物が添加される組成物内で架橋剤化合物が均一に分散することにより、それから優れた架橋効果を有することを実験を通して確認して、発明を完成させた。 As the cross-linking agent compound according to the present invention is represented by the above chemical formula 1, the present inventors end the hydroxy group (-OH), which is a cross-linking functional group, with a specific functional group of R 1 and R 2. When substituted, the functional groups of R 1 and R 2 act as protective groups to increase the solubility and dispersibility of the cross-linking agent compound, and the cross-linking agent compound becomes uniform in the composition to which the cross-linking agent compound is added. By dispersing, it was confirmed through experiments that it had an excellent cross-linking effect, and the invention was completed.
また、本発明者らは、前記架橋性官能基であるヒドロキシ基(−OH)の末端をR1およびR2のケイ素含有官能基に置換する場合、ケイ素含有官能基を含むことによって既存のヒドロキシ基(−OH)末端の架橋剤よりも初期乾燥工程での架橋剤の反応性が低下し、熱処理後に架橋反応が開始されて架橋剤による初期物性の低下を減らすことを確認した。 Further, when the terminal of the hydroxy group (-OH) which is the crosslinkable functional group is replaced with the silicon-containing functional group of R 1 and R 2 , the present inventors include the existing hydroxy by containing the silicon-containing functional group. It was confirmed that the reactivity of the cross-linking agent in the initial drying step was lower than that of the cross-linking agent at the terminal (-OH), and the cross-linking reaction was started after the heat treatment to reduce the deterioration of the initial physical properties due to the cross-linking agent.
前記架橋剤化合物の架橋性官能基末端に導入されたR1およびR2の官能基は、感光性組成物内では架橋性官能基による架橋反応を抑制させて不必要な架橋構造の形成を最少化して、組成物の安定性および信頼性を向上させることができ、感光材料合成時に熱処理によってほぼ80℃以上の温度で着脱、除去されながら、架橋性官能基末端のヒドロキシ基が回復して円滑な架橋反応を行い、感光材料の機械的物性を向上させることができる。 The functional groups of R 1 and R 2 introduced into the terminal of the cross-linking functional group of the cross-linking agent compound suppress the cross-linking reaction by the cross-linking functional group in the photosensitive composition and minimize the formation of an unnecessary cross-linking structure. The stability and reliability of the composition can be improved, and the hydroxy group at the end of the crosslinkable functional group recovers smoothly while being attached and detached and removed at a temperature of about 80 ° C. or higher by heat treatment during the synthesis of the photosensitive material. The cross-linking reaction can be carried out to improve the mechanical properties of the photosensitive material.
つまり、感光性組成物内では上記化学式1で表される架橋剤化合物の構造を維持して、少なくとも1つ以上のカルボキシル基を含む高分子と上記化学式1で表される架橋剤化合物との架橋反応を抑制することができる。また、感光性組成物から感光材料を製造する乾燥工程、露光工程、硬化工程などを経て、熱処理により温度の上昇時に上記化学式1で表される架橋剤化合物においてR1およびR2の官能基が水素原子で置換されながら、少なくとも1つ以上のカルボキシル基を含む高分子と後述する化学式6で表される架橋剤化合物との間の架橋反応が進行することができる。 That is, in the photosensitive composition, the structure of the cross-linking agent compound represented by the above chemical formula 1 is maintained, and the polymer containing at least one or more carboxyl groups and the cross-linking agent compound represented by the above chemical formula 1 are crosslinked. The reaction can be suppressed. Further, the functional groups of R 1 and R 2 are contained in the cross-linking agent compound represented by the above chemical formula 1 when the temperature rises due to heat treatment through a drying step, an exposure step, a curing step, etc. for producing a photosensitive material from the photosensitive composition. The cross-linking reaction between the polymer containing at least one or more carboxyl groups and the cross-linking agent compound represented by the chemical formula 6 described later can proceed while being substituted with a hydrogen atom.
したがって、前記一実施形態の感光性組成物は、組成物中に添加される架橋剤化合物の架橋反応性を抑制して架橋剤化合物と少なくとも1つ以上のカルボキシル基を含む高分子の分散性を十分に向上させることができ、後述する他の実施形態の感光材料の製造過程中に組成物内で架橋剤化合物と少なくとも1つ以上のカルボキシル基を含む高分子間架橋反応を通して感光材料の強度を向上させる効果を実現することができる。 Therefore, the photosensitive composition of the above embodiment suppresses the cross-linking reactivity of the cross-linking agent compound added to the composition to improve the dispersibility of the cross-linking agent compound and the polymer containing at least one carboxyl group. The strength of the photosensitive material can be sufficiently improved and the strength of the photosensitive material is increased through an interpolymer cross-linking reaction containing a cross-linking agent compound and at least one carboxyl group in the composition during the production process of the photosensitive material of another embodiment described later. The effect of improving can be realized.
1.架橋剤化合物
本発明に係る架橋剤化合物は、上記化学式1で表される特定の化学構造を有することができる。前記架橋剤化合物の物理/化学的特性は、上述した化学式1の特定構造に起因すると考えられる。
1. 1. Crosslinking agent compound The crosslinking agent compound according to the present invention can have a specific chemical structure represented by the above chemical formula 1. The physical / chemical properties of the cross-linking agent compound are considered to be due to the specific structure of Chemical Formula 1 described above.
上記化学式1中、Aは、1価〜4価の芳香族官能基であり、jは1〜4の整数である。前記Aは、架橋剤化合物の中心に位置する芳香族官能基であり、Aに含まれている末端官能基に化学式1中の中括弧'[]'で表される官能基がj個ほど結合することができる。 In the above chemical formula 1, A is a monovalent to tetravalent aromatic functional group, and j is an integer of 1 to 4. A is an aromatic functional group located at the center of the cross-linking agent compound, and about j functional groups represented by curly braces'[]' in Chemical Formula 1 are bonded to the terminal functional group contained in A. can do.
つまり、上記化学式1中、jが1であれば、Aは1価の官能基である。また、jが2であれば、Aは2価の官能基である。また、jが3であれば、Aは3価の官能基である。また、jが4であれば、Aは4価の官能基である。 That is, if j is 1 in the above chemical formula 1, A is a monovalent functional group. If j is 2, A is a divalent functional group. If j is 3, A is a trivalent functional group. If j is 4, A is a tetravalent functional group.
好ましくは、上記化学式1中、Aは炭素数6〜30のアリーレン基であり、jは2である。 Preferably, in the above chemical formula 1, A is an arylene group having 6 to 30 carbon atoms, and j is 2.
上記化学式1で表される架橋剤化合物のように、Aで表示される架橋剤化合物の中心に位置する官能基が芳香族官能基の場合、脂肪族官能基が中心に位置する架橋剤化合物に比べて耐熱性および寸法安定性を向上させることができる。これは、芳香族官能基が含まれることによって、分子間引力および硬直性が増加するためである。 When the functional group located at the center of the cross-linking agent compound represented by A is an aromatic functional group like the cross-linking agent compound represented by the chemical formula 1, the cross-linking agent compound in which the aliphatic functional group is located at the center Compared with this, heat resistance and dimensional stability can be improved. This is because the inclusion of aromatic functional groups increases intermolecular attractive force and rigidity.
より具体的には、上記化学式1中、Aは下記化学式2で表される2価の芳香族官能基であり、jは2である。
[化学式2]
[Chemical formula 2]
上記化学式1中、L1およびL2は、それぞれ独立して、炭素数1〜10のアルキレン基または炭素数6〜20のアリーレン基のうちの一つであり、好ましくは、L1およびL2は、それぞれ独立して、炭素数1〜5のアルキレン基、例えばエチレン基であってもよい。 In the above chemical formula 1, L 1 and L 2 are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and L 1 and L 2 are preferable. May be independently alkylene groups having 1 to 5 carbon atoms, for example, ethylene groups.
上記化学式1中、R1およびR2は、前記架橋剤化合物の架橋性官能基であるヒドロキシ基(−OH)末端に水素原子の代わりに置換された官能基であって、少なくとも1つ以上のカルボキシル基を含む高分子と上記化学式1で表される架橋剤化合物との架橋反応を抑制させることができる。 In the above chemical formula 1, R 1 and R 2 are functional groups in which the hydroxy group (-OH) terminal, which is a cross-linking functional group of the cross-linking agent compound, is substituted instead of a hydrogen atom, and at least one or more. It is possible to suppress the cross-linking reaction between the polymer containing a carboxyl group and the cross-linking agent compound represented by the above chemical formula 1.
後述するように、前記R1およびR2の官能基は、感光性組成物から感光材料を製造する乾燥工程、露光工程、硬化工程などを経て、ほぼ80℃以上の温度に上昇時、水素原子で置換され着脱することができることができる。 As will be described later, the functional groups of R 1 and R 2 are hydrogen atoms when the temperature rises to about 80 ° C. or higher through a drying step, an exposure step, a curing step, etc. for producing a photosensitive material from a photosensitive composition. It can be replaced with and attached / detached.
前記R1およびR2は、それぞれ独立して、ケイ素含有一価官能基であってもよい。 The R 1 and R 2 may be independently silicon-containing monovalent functional groups.
具体的には、前記ケイ素含有一価官能基は、下記化学式3で表される官能基であってもよい。
[化学式3]
[Chemical formula 3]
より具体的には、上記化学式3中、R5〜R7は炭素数1〜10のアルキル、好ましくは、メチル基またはエチル基であってもよい。 More specifically, in the above chemical formula 3, R 5 to R 7 may be an alkyl having 1 to 10 carbon atoms, preferably a methyl group or an ethyl group.
上記化学式1中、Aは2価の芳香族官能基であり、nは2である。つまり、上記化学式1で表される架橋剤化合物は、下記化学式1−1で表される化合物を含むことができる。
[化学式1−1]
[Chemical formula 1-1]
具体的には、上記化学式1−1中、A'は、炭素数6〜30のアリーレン基、より具体的には上記化学式2で表される2価の芳香族官能基であってもよい。 Specifically, in the above chemical formula 1-1, A'may be an arylene group having 6 to 30 carbon atoms, and more specifically, a divalent aromatic functional group represented by the above chemical formula 2.
また、上記化学式1−1中、L4〜L7は、それぞれ独立して、炭素数1〜10のアルキレン基または炭素数6〜20のアリーレン基のうちの一つであり、R3、R3'、R4、およびR4'は、それぞれ独立して、ケイ素含有一価官能基であってもよい。 Further, in the above chemical formula 1-1, L 4 to L 7 are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and are R 3 and R. 3 ', R 4, and R 4' are each independently, may be a silicon-containing monovalent functional group.
より具体的には、上記化学式1−1で表される架橋剤化合物の例としては、A'は、上記化学式2で表される2価の芳香族官能基であり、L4〜L7は、すべて炭素数2のエチレン基であり、R3〜R6は、すべて上記化学式3で表される官能基(R3、R3'、R4、およびR4'はメチル基)である、下記化学式1−2で表される化合物が挙げられる。
[化学式1−2]
[Chemical formula 1-2]
また、上記化学式1−1で表される架橋剤化合物の他の例としては、A'は、上記化学式2で表される2価の芳香族官能基であり、L4〜L7は、すべて炭素数2のエチレン基であり、R3〜R6は、すべて上記化学式3で表される官能基(R3、R3'、R4、およびR4'はエチル基)である、下記化学式1−3で表される化合物が挙げられる。
[化学式1−3]
[Chemical formula 1-3]
一方、上記化学式1で表される架橋剤化合物は、溶媒に対する溶解性に優れて、溶媒に前記架橋剤化合物を添加した後、10秒間混合する混合溶液は透明であることができる。 On the other hand, the cross-linking agent compound represented by the above chemical formula 1 is excellent in solubility in a solvent, and the mixed solution to be mixed for 10 seconds after adding the cross-linking agent compound to the solvent can be transparent.
前記混合溶液は、上記化学式1で表される架橋剤化合物と溶媒との混合物である。前記溶媒の例は特に限定されず、感光性組成物に含まれている溶媒として、例えば、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドン、N−メチルカプロラクタム、2−ピロリドン、N−エチルピロリドン、N−ビニルピロリドン、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ−ブチロラクトン、3−メトキシ−N,N−ジメチルプロパンアミド、3−エトキシ−N,N−ジメチルプロパンアミド、3−ブトキシ−N,N−ジメチルプロパンアミド、1,3−ジメチル−イミダゾリジノン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、ジグライム、4−ヒドロキシ−4−メチル−2−ペンタノン、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテル、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノイソプロピルエーテルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテルアセテートなどが挙げられる。これらは単独で用いられてもよく、混合して用いられてもよい。 The mixed solution is a mixture of the cross-linking agent compound represented by the above chemical formula 1 and a solvent. Examples of the solvent are not particularly limited, and examples of the solvent contained in the photosensitive composition include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam. , 2-Pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethylamyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone , Ethylene carbonate, propylene carbonate, jiglime, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether , Ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate and the like. These may be used alone or in combination.
前記混合溶液で、上記化学式1で表される架橋剤化合物は、前記混合溶液全体重量を基準にして1重量%〜30重量%、または2重量%〜25重量%、または10重量%〜25重量%、または10重量%超過25重量%以下含まれ得る。 In the mixed solution, the cross-linking agent compound represented by the chemical formula 1 is 1% by weight to 30% by weight, or 2% by weight to 25% by weight, or 10% by weight to 25% by weight based on the total weight of the mixed solution. %, Or 10% by weight and 25% by weight or less.
一方、本発明の一実施形態によれば、上記化学式1で表される架橋剤化合物は、感光材料用途に用いることができる。 On the other hand, according to one embodiment of the present invention, the cross-linking agent compound represented by the above chemical formula 1 can be used for photosensitive material applications.
具体的には、上記化学式1で表される架橋剤化合物は、フォトレジスト、配向膜、接着剤、絶縁層、ディスプレイ装置のカラーフィルター、ディスプレイ装置のブラックマトリックス、ディスプレイ装置のカラムスペーサ、光硬化性塗料、光硬化性インクなどの製造に用いることができる。 Specifically, the cross-linking agent compound represented by the above chemical formula 1 is a photoresist, an alignment film, an adhesive, an insulating layer, a color filter of a display device, a black matrix of a display device, a column spacer of a display device, and a photocurable property. It can be used in the production of paints, photocurable inks and the like.
上記化学式1で表される架橋剤化合物は、上述したように、溶解度に優れ、末端に導入された官能基が80℃以上の温度で熱処理される場合、着脱、除去されながら架橋性官能基末端のヒドロキシ基が回復して円滑な架橋反応を進行することができ、このような本発明の架橋剤化合物の特徴は、上記化学式1で表される特定構造を有することによって具現され得る。 As described above, the cross-linking agent compound represented by the above chemical formula 1 has excellent solubility, and when the functional group introduced at the terminal is heat-treated at a temperature of 80 ° C. or higher, the cross-linking functional group terminal is detached and removed while being attached and detached. The hydroxy group of the above can be recovered and a smooth cross-linking reaction can proceed, and such characteristics of the cross-linking agent compound of the present invention can be realized by having a specific structure represented by the above chemical formula 1.
このような特徴によって、上記化学式1で表される架橋剤化合物を感光材料の用途に使用する場合、前記架橋剤化合物が感光性組成物中に均一に分散して、それから製造される感光材料の物性を均一にすることができる。 Due to these characteristics, when the cross-linking agent compound represented by the above chemical formula 1 is used as a photosensitive material, the cross-linking agent compound is uniformly dispersed in the photosensitive composition, and the photosensitive material produced from the cross-linking agent compound is uniformly dispersed. Physical properties can be made uniform.
また、感光材料の製造過程で、常温では架橋反応性を抑制して、架橋剤化合物と少なくとも1つ以上のカルボキシル基を含む高分子の分散性を十分に向上させると同時に、感光材料を製造する乾燥工程、露光工程、硬化工程などを経て、80℃以上の温度に上昇することによって、架橋性官能基末端のヒドロキシ基が回復して少なくとも1つ以上のカルボキシル基を含む高分子間架橋反応が進行することによって、機械的強度が向上した感光材料を実現することができる。 Further, in the process of manufacturing the photosensitive material, the cross-linking reactivity is suppressed at room temperature to sufficiently improve the dispersibility of the cross-linking agent compound and the polymer containing at least one or more carboxyl groups, and at the same time, the photosensitive material is manufactured. By raising the temperature to 80 ° C. or higher through a drying step, an exposure step, a curing step, etc., the hydroxy group at the terminal of the crosslinkable functional group is recovered and the interpolymer crosslinking reaction containing at least one or more carboxyl groups is carried out. By advancing, it is possible to realize a photosensitive material having improved mechanical strength.
従来の架橋剤化合物は、溶解性が低く、架橋剤の安定性および分散性が低下し、感光性組成物が均一でなくて信頼性が低下するなどの技術的な限界が存在したが、本発明により提供される上記化学式1の架橋剤化合物は、溶解性に優れているだけでなく、末端の導入された官能基が架橋性ヒドロキシ基を保護することによって、優れた機械的強度だけでなく、優れた貯蔵安定性および溶解性を有することができる。 Conventional cross-linking agent compounds have technical limitations such as low solubility, reduced stability and dispersibility of the cross-linking agent, and non-uniformity of the photosensitive composition, resulting in reduced reliability. The cross-linking agent compound of the above chemical formula 1 provided by the invention is not only excellent in solubility, but also has excellent mechanical strength due to the fact that the introduced functional group at the terminal protects the cross-linking hydroxy group. , Can have excellent storage stability and solubility.
2.感光性組成物
一方、本発明の一実施形態によれば、上記化学式1で表される架橋剤化合物を含む、感光性組成物が提供され得る。
2. Photosensitive composition On the other hand, according to one embodiment of the present invention, a photosensitive composition containing a cross-linking agent compound represented by the above chemical formula 1 can be provided.
また、本発明の一実施形態によれば、上記化学式1で表される架橋剤化合物および少なくとも1つ以上のカルボキシル基を含む高分子を含む、感光性組成物が提供され得る。 Further, according to one embodiment of the present invention, a photosensitive composition containing a cross-linking agent compound represented by the above chemical formula 1 and a polymer containing at least one or more carboxyl groups can be provided.
前記少なくとも1つ以上のカルボキシル基を含む高分子は特に限定されないが、例えば、ポリアミック酸などの高分子であってもよい。 The polymer containing at least one or more carboxyl groups is not particularly limited, and may be, for example, a polymer such as polyamic acid.
上記化学式1で表される架橋剤化合物は、感光性組成物全体重量を基準にして1重量%〜30重量%、または2重量%〜25重量%、または10重量%〜25重量%、または10重量%超過25重量%以下含まれ得る。 The cross-linking agent compound represented by the above chemical formula 1 is 1% by weight to 30% by weight, or 2% by weight to 25% by weight, or 10% by weight to 25% by weight, or 10% by weight, based on the total weight of the photosensitive composition. May be over 25% by weight and up to 25% by weight.
前記架橋剤化合物の含有量が多すぎると、前記少なくとも1つ以上のカルボキシル基を含む高分子の架橋度が増加しすぎることによって、前記高分子の柔軟性が減少することができ、組成物の粘度増加による貯蔵安定性の低下および組成物中の架橋剤分散性の低下、または組成物中でのゲル化反応により基板への塗布性が減少することができる。 If the content of the cross-linking agent compound is too large, the degree of cross-linking of the polymer containing at least one or more carboxyl groups increases too much, so that the flexibility of the polymer can be reduced, and the composition can be composed. The coatability to a substrate can be reduced by a decrease in storage stability due to an increase in viscosity, a decrease in the dispersibility of a cross-linking agent in the composition, or a gelation reaction in the composition.
反面、前記架橋剤化合物の含有量が少なすぎると、前記少なくとも1つ以上のカルボキシル基を含む高分子の架橋度増加による機械的強度の向上効果が十分に具現できない場合もある。 On the other hand, if the content of the cross-linking agent compound is too small, the effect of improving the mechanical strength by increasing the degree of cross-linking of the polymer containing at least one or more carboxyl groups may not be sufficiently realized.
上記化学式1で表される架橋剤化合物は、一定水準以上の温度、具体的には80℃以上の温度で熱処理される場合、R1およびR2の官能基が着脱、除去されながら、ヒドロキシ基(OH基)の架橋官能基末端が回復して、前記少なくとも1つ以上のカルボキシル基を含む高分子と円滑な架橋反応を起こすことができる。 When the cross-linking agent compound represented by the above chemical formula 1 is heat-treated at a temperature above a certain level, specifically, at a temperature of 80 ° C. or higher, the hydroxy groups are removed while the functional groups of R 1 and R 2 are attached and detached. The cross-linking functional group terminal of the (OH group) is restored, and a smooth cross-linking reaction can occur with the polymer containing at least one or more carboxyl groups.
ただし、80℃未満の常温および常圧の条件で、前記R1およびR2の官能基の一部または全部が水素原子で置換されて、少なくとも2以上の末端架橋官能基が露出した架橋剤化合物が一部含まれ得る。 However, under normal temperature and pressure conditions of less than 80 ° C., a cross-linking agent compound in which some or all of the functional groups of R 1 and R 2 are substituted with hydrogen atoms and at least two or more terminal cross-linking functional groups are exposed. May be included in part.
これは、前記一実施形態の感光性組成物に含まれる前記少なくとも1つ以上のカルボキシル基を含む高分子によるものである。具体的には、前記少なくとも1つ以上のカルボキシル基を含む高分子を含むことによって、感光性組成物が前記R1およびR2の官能基が着脱しやすい酸性条件を示して、前記R1およびR2の官能基の一部または全部が水素原子で置換されて、少なくとも2以上の末端架橋官能基が露出した架橋剤化合物が一部含まれ得る。 This is due to the polymer containing at least one or more carboxyl groups contained in the photosensitive composition of the above embodiment. Specifically, by including the polymer containing at least one or more carboxyl groups, the photosensitive composition exhibits acidic conditions in which the functional groups of R 1 and R 2 are easily attached and detached, and the R 1 and A cross-linking agent compound in which some or all of the functional groups of R 2 are substituted with hydrogen atoms and at least two or more terminal cross-linking functional groups are exposed may be contained.
つまり、前記一実施形態による感光性組成物は、少なくとも2以上の末端架橋官能基が露出した架橋剤化合物をさらに含むことができる。 That is, the photosensitive composition according to the above embodiment can further contain a cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed.
具体的には、前記少なくとも2以上の末端架橋官能基が露出した架橋剤化合物は、下記化学式4で表される架橋剤化合物であってもよい。
[化学式4]
[Chemical formula 4]
上記化学式4中、A''は1価〜4価の官能基であり、aは1〜4の整数であり、bは0〜3の整数であり、aとbの合計は1〜4であり、L8〜L11は、それぞれ独立して、炭素数1〜10のアルキレン基または炭素数6〜20のアリーレン基のうちの一つであり、R21およびR22のうち少なくとも一つは水素であり、残りはケイ素含有一価官能基であり、R23およびR24は、それぞれ独立して、ケイ素含有一価官能基である。 In the above chemical formula 4, A'' is a monovalent to tetravalent functional group, a is an integer of 1 to 4, b is an integer of 0 to 3, and the sum of a and b is 1 to 4. Yes, L 8 to L 11 are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and at least one of R 21 and R 22 is. It is hydrogen, the rest is a silicon-containing monovalent functional group, and R 23 and R 24 are independently silicon-containing monovalent functional groups.
より具体的には、上記化学式4中、R21およびR22がすべて水素の場合、aは1〜4であり、上記化学式4中、R23およびR24のうちの一つが水素であり、残りはケイ素含有一価官能基の場合、aは2〜4である。 More specifically, when R 21 and R 22 are all hydrogen in the above chemical formula 4, a is 1 to 4, one of R 23 and R 24 in the above chemical formula 4 is hydrogen, and the rest. Is a silicon-containing monovalent functional group, where a is 2-4.
前記少なくとも2以上の末端架橋官能基が露出した架橋剤化合物を含むことによって、前記一実施形態による感光性組成物は、前記少なくとも1つ以上のカルボキシル基を含む高分子と少なくとも2以上の末端架橋官能基が露出した架橋剤化合物との間の架橋結合物を含むことができる。 By including the cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed, the photosensitive composition according to the above embodiment is subjected to at least two or more terminal cross-linking with the polymer containing at least one or more carboxyl groups. It can include cross-linking conjugates with cross-linking agent compounds with exposed functional groups.
一方、前記一実施形態による感光性組成物は、上記化学式1で表される架橋剤化合物100重量部に対し、上記化学式4で表される架橋剤化合物を0.001重量部〜10重量部、0.1重量部〜10重量部、0.1重量部〜5重量部、または0.1重量部〜3重量部含むことができる。 On the other hand, in the photosensitive composition according to the above embodiment, 0.001 part by weight to 10 parts by weight of the cross-linking agent compound represented by the above-mentioned chemical formula 4 is used with respect to 100 parts by weight of the cross-linking agent compound represented by the above-mentioned chemical formula 1. It can include 0.1 parts by weight to 10 parts by weight, 0.1 parts by weight to 5 parts by weight, or 0.1 parts by weight to 3 parts by weight.
前記一実施形態の感光性組成物が、上記化学式4で表される架橋剤化合物をこのような範囲を満たすように含有する場合、少なくとも1つ以上のカルボキシル基を含む高分子との架橋結合反応を起こすことができる少なくとも2以上の末端架橋官能基が露出した架橋剤化合物が感光性組成物中に少量含まれて、長期保存安定性および信頼性の向上により感光性組成物から製造される感光材料の物性を向上させるだけでなく、成膜工程の効率性が顕著に向上する効果を実現することができる。 When the photosensitive composition of the above embodiment contains a cross-linking agent compound represented by the above chemical formula 4 so as to satisfy such a range, a cross-linking reaction with a polymer containing at least one or more carboxyl groups. A cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed is contained in the photosensitive composition in a small amount, and the photosensitive composition is produced from the photosensitive composition by improving long-term storage stability and reliability. Not only can the physical properties of the material be improved, but also the effect of significantly improving the efficiency of the film forming process can be realized.
反面、感光性組成物が上記化学式4で表される架橋剤化合物を上述した範囲から外れるように含有する場合、長期保存時、少なくとも2以上の末端架橋官能基が露出した架橋剤化合物が感光性組成物中に多量含まれることになり、少なくとも1つ以上のカルボキシル基を含む高分子および前記少なくとも2以上の末端架橋官能基が露出した架橋剤化合物の架橋結合反応が起こり、副産物が多数形成され、それから製造される感光材料の貯蔵安定性が低下して、長期保存には不適である。 On the other hand, when the photosensitive composition contains the cross-linking agent compound represented by the above chemical formula 4 so as to be outside the above-mentioned range, the cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed is photosensitive during long-term storage. A large amount is contained in the composition, and a cross-linking reaction occurs between the polymer containing at least one carboxyl group and the cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed, and a large number of by-products are formed. , The storage stability of the photosensitive material produced from it is reduced, which makes it unsuitable for long-term storage.
一方、前記感光性組成物は、下記化学式5で表される化合物をさらに含むことができる。
[化学式5]
[Chemical formula 5]
上記化学式5中、R5〜R7は上記化学式3で定義した通りである。 In the above chemical formula 5, R 5 to R 7 are as defined in the above chemical formula 3.
上記化学式5で表される化合物は、上記化学式1で表される架橋剤化合物の置換反応の結果物であり得る。 The compound represented by the chemical formula 5 may be the result of a substitution reaction of the cross-linking agent compound represented by the chemical formula 1.
具体的には、上記化学式1で表される架橋剤化合物においてR1およびR2の官能基は、置換反応によってR1およびR2の官能基の全部または一部が着脱でき、これにより、前記少なくとも2以上の末端架橋官能基が露出した架橋剤化合物および上記化学式5で表される化合物を形成することができる。 Specifically, the functional group of R 1 and R 2 in the crosslinking compound represented by Formula 1 can detachably all or part of the functional groups R 1 and R 2 by substitution reaction, thereby, the It is possible to form a cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed and a compound represented by the above chemical formula 5.
一方、前記少なくとも1つ以上のカルボキシル基を含む高分子は、ポリアミック酸(共)重合体を含むことができる。 On the other hand, the polymer containing at least one or more carboxyl groups can contain a polyamic acid (co) polymer.
具体的には、前記少なくとも1つ以上のカルボキシル基を含む高分子は、下記化学式6で表される繰り返し単位を含む第1ポリアミック酸(共)重合体、および下記化学式7で表される繰り返し単位を含む第2ポリアミック酸(共)重合体を含むことができる。
[化学式6]
[化学式8]
[化学式9]
[化学式10]
[Chemical formula 6]
[Chemical formula 8]
[Chemical formula 9]
[Chemical formula 10]
また、前記少なくとも1つ以上のカルボキシル基を含む高分子で、上記化学式6で表される繰り返し単位を含む第1ポリアミック酸(共)重合体は、下記化学式12で表される繰り返し単位および下記化学式13で表される繰り返し単位からなる群から選択される1種以上の繰り返し単位をさらに含むことができる。
[化学式12]
[Chemical formula 12]
つまり、第1ポリアミック酸(共)重合体は、上記化学式6で表される単一の繰り返し単位からなる単独重合体、または上記化学式6で表される繰り返し単位に加えて、上記化学式12で表される繰り返し単位および上記化学式13で表される繰り返し単位からなる群から選択される1種以上の繰り返し単位をさらに含む複合重合体である共重合体であってもよい。 That is, the first polyamic acid (co) polymer is represented by the above chemical formula 12 in addition to the homopolymer composed of a single repeating unit represented by the above chemical formula 6 or the repeating unit represented by the above chemical formula 6. It may be a copolymer which is a composite polymer further containing one or more kinds of repeating units selected from the group consisting of a repeating unit to be carried over and a repeating unit represented by the above chemical formula 13.
また、前記少なくとも1つ以上のカルボキシル基を含む高分子で、上記化学式7で表される繰り返し単位を含む第2ポリアミック酸(共)重合体は、下記化学式14で表される繰り返し単位および下記化学式15で表される繰り返し単位からなる群から選択される1種以上の繰り返し単位をさらに含むことができる。
[化学式14]
[Chemical formula 14]
つまり、第2ポリアミック酸(共)重合体は、上記化学式7で表される単一の繰り返し単位からなる単独重合体、または上記化学式7で表される繰り返し単位に加えて、上記化学式14で表される繰り返し単位および上記化学式15で表される繰り返し単位からなる群から選択される1種以上の繰り返し単位をさらに含む複合重合体である共重合体であってもよい。 That is, the second polyamic acid (co) polymer is represented by the above chemical formula 14 in addition to the homopolymer composed of a single repeating unit represented by the above chemical formula 7 or the repeating unit represented by the above chemical formula 7. It may be a copolymer which is a composite polymer further containing one or more kinds of repeating units selected from the group consisting of a repeating unit to be carried over and a repeating unit represented by the above chemical formula 15.
具体的には、前記第1ポリアミック酸(共)重合体は、上記化学式6で表される繰り返し単位を必ず含み、上記化学式12で表される繰り返し単位および上記化学式13で表される繰り返し単位のうちの1種またはこれらの組み合わせをさらに含むことができる。 Specifically, the first polyamic acid (co) polymer always contains the repeating unit represented by the above chemical formula 6, and the repeating unit represented by the above chemical formula 12 and the repeating unit represented by the above chemical formula 13. One of them or a combination thereof can be further included.
具体的には、前記第2ポリアミック酸(共)重合体は、上記化学式7で表される繰り返し単位を必ず含み、上記化学式14で表される繰り返し単位および上記化学式15で表される繰り返し単位のうちの1種またはこれらの組み合わせをさらに含むことができる。 Specifically, the second polyamic acid (co) polymer always contains the repeating unit represented by the above chemical formula 7, and the repeating unit represented by the above chemical formula 14 and the repeating unit represented by the above chemical formula 15. One of them or a combination thereof can be further included.
前記一実施形態による感光性組成物中の第1ポリアミック酸(共)重合体および第2ポリアミック酸(共)重合体において、X1〜X6は、それぞれ独立して、上記化学式8で表される4価の有機基であってもよい。前記X1〜X6は、ポリアミック酸、ポリアミック酸エステル、またはポリイミドの合成時に使用されるテトラカルボン酸二無水物化合物に由来する官能基であってもよい。 In the first polyamic acid (co) polymer and the second polyamic acid (co) polymer in the photosensitive composition according to the above embodiment, X 1 to X 6 are independently represented by the above chemical formula 8. It may be a tetravalent organic group. The X 1 to X 6 may be a functional group derived from a polyamic acid, a polyamic acid ester, or a tetracarboxylic dianhydride compound used in the synthesis of polyimide.
上記化学式8中、R13〜R18は、それぞれ独立して、水素または炭素数1〜6のアルキル基であり、L'は、単一結合、−O−、−CO−、−COO−、−S−、−SO−、−SO2−、−CR19R20−、−(CH2)Z−、−O(CH2)ZO−、−COO(CH2)ZOCO−、−CONH−、またはフェニレンの中から選択されるいずれか一つであり、前記L'中のR19およびR20は、それぞれ独立して、水素、炭素数1〜10のアルキル基または炭素数1〜10のハロアルキル基であり、前記L'中のzは、1〜10の整数である。 In the above chemical formula 8, R 13 to R 18 are each independently an alkyl group having hydrogen or 1 to 6 carbon atoms, and L'is a single bond, −O−, −CO−, −COO−, respectively. -S -, - SO -, - SO 2 -, - CR 19 R 20 -, - (CH 2) Z -, - O (CH 2) Z O -, - COO (CH 2) Z OCO -, - CONH -Or one selected from phenylene, and R 19 and R 20 in the L'are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, respectively. Is a haloalkyl group of, and z in the L'is an integer of 1 to 10.
より好ましくは、前記X1〜X6は、それぞれ独立して、シクロブタン−1,2,3,4−テトラカルボン酸二無水物に由来する下記化学式8−1の有機基、1,3−ジメチルシクロブタン−1,2,3,4−テトラカルボン酸二無水物に由来する下記化学式8−2の有機基、テトラヒドロ−[3,3'−ビフラン]−2,2',5,5'−テトラオンに由来する下記化学式8−3の有機基、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物から由来する下記化学式8−4の有機基、ピロメリット酸二無水物に由来する下記化学式8−5の有機基、または3,3',4,4'−ビフェニルテトラカルボン酸二無水物に由来する下記化学式8−6の有機基であってもよい。
[化学式8−1]
[Chemical formula 8-1]
一方、前記一実施形態による感光性組成物のうち、第1ポリアミック酸(共)重合体は、上記化学式6または化学式12〜13の繰り返し単位でY1〜Y3がそれぞれ独立して、上記化学式9で表される2価の有機基であってもよい。前記第1ポリアミック酸(共)重合体がすでにイミド化されたイミド繰り返し単位を含むジアミンから合成されるので、塗膜形成後、高温の熱処理工程なしに直ちに光を照射して異方性を生成させ、以降に熱処理を進行して配向膜を完成することができるため、光照射エネルギーを大幅に減らすことができるだけでなく、1回の熱処理工程を含む簡単な工程でも配向性および安定性に優れるだけでなく、電圧維持保全率と電気的特性にも優れた感光材料を製造することができる。 On the other hand, of the photosensitive composition according to an embodiment, the first polyamic acid (co) polymer is Y 1 to Y 3 in the repeating unit of Formula 6 or Formula 12 to 13 are each independently the chemical formula It may be a divalent organic group represented by 9. Since the first polyamic acid (co) polymer is synthesized from a diamine containing an already imidized imide repeating unit, it is immediately irradiated with light after forming a coating film without a high-temperature heat treatment step to generate anisotropy. Since the alignment film can be completed by proceeding with the heat treatment thereafter, not only the light irradiation energy can be significantly reduced, but also the orientation and stability are excellent even in a simple process including one heat treatment step. Not only that, it is possible to produce a photosensitive material having excellent voltage maintenance and maintenance rate and electrical characteristics.
具体的には、上記化学式9中、Tは、下記化学式8−1で表される官能基または下記8−2で表される官能基であってもよい。
[化学式8−1]
[Chemical formula 8-1]
より具体的には、上記化学式9で表される有機基の例は特に限定されるものではないが、例えば、下記化学式9−1または化学式9−2で表される官能基であってもよい。
[化学式9−1]
[Chemical formula 9-1]
前記第1ポリアミック酸(共)重合体において上記化学式6で表される繰り返し単位を全体繰り返し単位に対し、5モル%〜74モル%、または10モル%〜60モル%含むことができる。 In the first polyamic acid (co) polymer, the repeating unit represented by the above chemical formula 6 can be contained in an amount of 5 mol% to 74 mol% or 10 mol% to 60 mol% with respect to the total repeating unit.
上述のように、上記化学式6で表されるイミド繰り返し単位を特定の含有量で含む重合体を利用すれば、前記第1ポリアミック酸(共)重合体が既にイミド化されたイミド繰り返し単位を一定の含有量で含むので、高温の熱処理工程を省略し、直ちに光を照射しても安定性に優れた感光材料を製造することができる。 As described above, if a polymer containing the imide repeating unit represented by the chemical formula 6 in a specific content is used, the imide repeating unit in which the first polyamic acid (co) polymer has already been imidized is constant. Since it is contained in the content of, it is possible to omit the high-temperature heat treatment step and produce a photosensitive material having excellent stability even if it is immediately irradiated with light.
つまり、上記化学式6で表される繰り返し単位をこのような含有量範囲で含むことが保管安定性に優れた感光性重合体を提供できるので好ましい。 That is, it is preferable that the repeating unit represented by the above chemical formula 6 is contained in such a content range because a photosensitive polymer having excellent storage stability can be provided.
また、上記化学式12で表される繰り返し単位または化学式13で表される繰り返し単位は、目的とする特性に応じて適切な含有量で含まれてもよい。 Further, the repeating unit represented by the chemical formula 12 or the repeating unit represented by the chemical formula 13 may be contained in an appropriate content according to the desired characteristics.
一方、本発明の一実施形態による感光性組成物のうち、第2ポリアミック酸(共)重合体は、上記化学式7または上記化学式14〜15の繰り返し単位でY4〜Y6がそれぞれ独立して、上記化学式10で表される2価の有機基であってもよい。前記Y4、Y5、Y6は、上記化学式10で表される2価の有機基と定義され、上記効果を示すことができる多様な構造の感光性重合体を提供することができる。 On the other hand, of the photosensitive composition according to an embodiment of the present invention, the second polyamic acid (co) polymer, Y 4 to Y 6 in the repeating unit of Formula 7 or Chemical Formula 14 to 15 are each independently , It may be a divalent organic group represented by the above chemical formula 10. The Y 4 , Y 5 , and Y 6 are defined as divalent organic groups represented by the chemical formula 10, and can provide photosensitive polymers having various structures capable of exhibiting the above effects.
上記化学式10中、A'は15族元素であり、前記15族元素は、窒素(N)、リン(P)、ヒ素(As)、スズ(Sn)またはビスマス(Bi)であってもよい。前記R'は、前記Aに結合する官能基であって、aで表される数字の個数ほどA'元素に結合することができる。好ましくは、上記化学式10中、A'は窒素であり、R'は水素であり、aは1である。 In the above chemical formula 10, A'is a group 15 element, and the group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), tin (Sn) or bismuth (Bi). The R'is a functional group bonded to the A, and can be bonded to the A'element as many as the number represented by a. Preferably, in the above chemical formula 10, A'is nitrogen, R'is hydrogen, and a is 1.
一方、上記化学式10中、Z1〜Z4のうち少なくとも一つは窒素であり、残りは炭素であるという条件を満たすため、前記窒素原子により上記化学式10は、中心点または中心線を基準にして対称でない非対称構造を形成してもよい。上記化学式10は、感光性重合体の形成に使用される前駆体である窒素原子などを含む特定構造のジアミンに由来する繰り返し単位であって、後述する非対称ジアミンの使用によるものと考えられる。 On the other hand, in the chemical formula 10, at least one of Z 1 to Z 4 is nitrogen, because the condition that the remainder being carbon, the formula 10 by the nitrogen atom, based on the center point or center line May form an asymmetric structure that is not symmetrical. The chemical formula 10 is a repeating unit derived from a diamine having a specific structure containing a nitrogen atom or the like, which is a precursor used for forming a photosensitive polymer, and is considered to be due to the use of an asymmetric diamine described later.
上記化学式10で表される有機基は、2級アミン基または3級アミン基を介して2個の芳香族環化合物、好ましくは、ヘテロ芳香族環化合物および芳香族環化合物が結合する構造的特徴を有する。 The organic group represented by the chemical formula 10 is a structural feature in which two aromatic ring compounds, preferably a heteroaromatic ring compound and an aromatic ring compound, are bonded to each other via a secondary amine group or a tertiary amine group. Has.
より具体的には、上記化学式10中、Z1〜Z4のうちの一つが窒素であり、残りは炭素であってもよく、または上記化学式15中、Z1またはZ3のうちの一つが窒素であり、残りは炭素であり、Z2およびZ4は炭素であってもよい。つまり、上記化学式10中、Z1〜Z4が含まれている芳香族環は、ピリジン(pyridine)構造を有することができる。 More specifically, in the above chemical formula 10, one of Z 1 to Z 4 may be nitrogen and the rest may be carbon, or in the above chemical formula 15, one of Z 1 or Z 3 may be. Nitrogen, the rest is carbon, and Z 2 and Z 4 may be carbon. That is, in the above chemical formula 10, the aromatic ring containing Z 1 to Z 4 can have a pyridine (pyridine) structure.
また、上記化学式10は、下記化学式10−1、化学式10−2および化学式10−3からなる群から選択される1種以上の官能基を含むことができる。
[化学式10−1]
[Chemical formula 10-1]
より具体的には、上記化学式10で表される有機基の例は特に限定されるものではないが、例えば、下記化学式10−4、化学式10−5および化学式10−6からなる群から選択される1種以上の官能基であってもよい。
[化学式10−4]
[Chemical formula 10-4]
一方、本発明の一実施形態による感光性組成物は、前記第1ポリアミック酸(共)重合体100重量部に対し、第2ポリアミック酸(共)重合体含有量が10重量部〜1,000重量部、または15重量部〜800重量部であることが好ましい。 On the other hand, the photosensitive composition according to the embodiment of the present invention has a content of 10 parts by weight to 1,000 parts by weight of the second polyamic acid (co) polymer with respect to 100 parts by weight of the first polyamic acid (co) polymer. It is preferably parts by weight, or 15 parts by weight to 800 parts by weight.
前記第1ポリアミック酸(共)重合体、および第2ポリアミック酸(共)重合体それぞれの重量平均分子量(GPC測定)は特に限定されるものではないが、例えば10,000g/mol〜200,000g/molであることが好ましい。 The weight average molecular weight (GPC measurement) of each of the first polyamic acid (co) polymer and the second polyamic acid (co) polymer is not particularly limited, but is, for example, 10,000 g / mol to 200,000 g. It is preferably / mol.
3.感光材料
一方、本発明のさらに他の実施形態によれば、前記一実施形態の感光性組成物の硬化物を含む感光材料が提供され得る。前記硬化物とは、前記一実施形態の感光性組成物の硬化工程を経て得られる物質を意味する。
3. 3. Photosensitive material On the other hand, according to still another embodiment of the present invention, a photosensitive material containing a cured product of the photosensitive composition of the above embodiment can be provided. The cured product means a substance obtained through the curing step of the photosensitive composition of the above embodiment.
前記感光材料の形態がフィルム、膜などで実現される場合、前記感光材料の厚さは特に限定されるものではないが、例えば0.01μm〜1,000μmの範囲内で自由に調節可能である。前記感光材料の厚さが特定の数値ほど増加または減少する場合、感光材料から測定される物性も一定の数値ほど変化することがある。 When the form of the photosensitive material is realized by a film, a film, or the like, the thickness of the photosensitive material is not particularly limited, but can be freely adjusted within the range of, for example, 0.01 μm to 1,000 μm. .. When the thickness of the photosensitive material increases or decreases by a specific value, the physical properties measured from the photosensitive material may also change by a certain value.
一方、感光材料の製造工程において、上記化学式1で表される架橋剤化合物のR1およびR2の官能基が水素原子で置換され着脱することができ、これにより、架橋反応を進行させることができる。 On the other hand, in the manufacturing process of the photosensitive material, the functional groups of R 1 and R 2 of the cross-linking agent compound represented by the above chemical formula 1 can be replaced with hydrogen atoms and attached / detached, whereby the cross-linking reaction can proceed. it can.
つまり、前記感光材料は、下記化学式11で表される架橋剤化合物と少なくとも1つ以上のカルボキシル基を含む高分子との組み合わせを含むことができる。
[化学式11]
[Chemical formula 11]
上記化学式11で表される架橋剤化合物と少なくとも1つ以上のカルボキシル基を含む高分子との組み合わせは、上記化学式11で表される架橋剤化合物に含まれる架橋性官能基であるヒドロキシ基(−OH)が少なくとも1つ以上のカルボキシル基を含む高分子に含まれるカルボキシル基(−COOH)のカルボニル基(−CO−)と結合して、エステル結合(−COO)を形成して作られる。 The combination of the cross-linking agent compound represented by the chemical formula 11 and the polymer containing at least one or more carboxyl groups is a hydroxy group (-) which is a cross-linking functional group contained in the cross-linking agent compound represented by the chemical formula 11. OH) is bonded to the carbonyl group (-CO-) of the carboxyl group (-COOH) contained in the polymer containing at least one or more carboxyl groups to form an ester bond (-COO).
前記一実施形態の感光性組成物に上記化学式11で表される架橋剤化合物が含まれる場合、組成物内で一部の架橋反応が進行することにより、架橋剤化合物が組成物中に均一に分散されにくく、貯蔵安定性も減少することになる。 When the photosensitive composition of the above embodiment contains a cross-linking agent compound represented by the above chemical formula 11, a part of the cross-linking reaction proceeds in the composition, so that the cross-linking agent compound becomes uniform in the composition. It is difficult to disperse and storage stability is also reduced.
反面、本発明は、感光性組成物内では上記化学式1で表される架橋剤化合物を添加して組成物内での架橋反応を抑制し、前記感光材料の製造工程で自発的に化学式1で表される架橋剤化合物が化学式11で表される架橋剤化合物に転換されるように誘導することができる。これにより、組成物は、架橋剤化合物の分散性および安全性を向上させることができ、感光材料は、架橋構造の形成により機械的強度の向上効果を実現することができる。 On the other hand, in the present invention, the cross-linking agent compound represented by the above chemical formula 1 is added in the photosensitive composition to suppress the cross-linking reaction in the composition, and the chemical formula 1 is voluntarily used in the manufacturing process of the photosensitive material. The cross-linking agent compound represented can be induced to be converted into the cross-linking agent compound represented by Chemical Formula 11. Thereby, the composition can improve the dispersibility and safety of the cross-linking agent compound, and the photosensitive material can realize the effect of improving the mechanical strength by forming the cross-linked structure.
具体的には、前記一実施形態による感光材料の例は特に限定されないが、例えば、フォトレジスト、配向膜、接着剤、絶縁層、ディスプレイ装置のカラーフィルター、ディスプレイ装置のブラックマトリックス、ディスプレイ装置のカラムスペーサ、光硬化性塗料、光硬化性インクなどが挙げられる。 Specifically, the example of the photosensitive material according to the above embodiment is not particularly limited, and for example, a photoresist, an alignment film, an adhesive, an insulating layer, a color filter of a display device, a black matrix of a display device, and a column of a display device are used. Examples include spacers, photocurable paints, photocurable inks and the like.
本発明によれば、溶解性に優れ、向上した架橋効果を有する架橋剤化合物、分散性が向上して高い信頼性を有することができ、感光材料合成時に優れた機械的強度を実現することができ、貯蔵安定性に優れた感光性組成物、およびこれを利用した感光材料が提供され得る。 According to the present invention, a cross-linking agent compound having excellent solubility and an improved cross-linking effect can have high dispersibility and high reliability, and excellent mechanical strength can be realized at the time of synthesizing a photosensitive material. It is possible to provide a photosensitive composition which can be obtained and has excellent storage stability, and a photosensitive material using the same.
本発明を下記の実施例でより詳細に説明する。ただし、下記の実施例は本発明を例示するものに過ぎず、本発明の内容が下記の実施例によって限定されるものではない。 The present invention will be described in more detail with reference to the following examples. However, the following examples merely exemplify the present invention, and the content of the present invention is not limited to the following examples.
<製造例および比較製造例> <Manufacturing example and comparative manufacturing example>
製造例1:架橋剤の製造
窒素雰囲気下でN4,N4,N4',N4'−テトラキス(2−ヒドロキシエチル)ビフェニル−4,4'−ジカルボキシアミド(N4,N4,N4',N4'−tetrakis(2−hydroxyethyl)biphenyl−4,4'−dicarboxamide、13.0g、31.3mmol)とトリエチルアミン(19.0g、187.8mmol)をジクロロメタン(200mL)に分散した後、化合物trimethylsilyl chloride(13.5g、125.2mmol)を投入して0℃で2時間、常温で16時間攪拌した。反応終了後、炭酸水素ナトリウム飽和水溶液(300ml)を加え、水溶液層をジクロロメタン(200mL)で2回抽出した。これを硫酸マグネシウム(10g)で処理して乾燥した。ろ過した濾液を濃縮してN4,N4,N4',N4'−テトラキス(2−(トリメチルシリルオキシ)エチル)ビフェニル−4,4'−ジカルボキシアミド(N4,N4,N4',N4'−tetrakis(2−(trimethylsilyloxy)ethyl)biphenyl−4,4'−dicarboxamide、17.5g、収率79.3%)を製造した。 N4, N4, N4', N4'-tetrakis (2-hydroxyethyl) biphenyl-4,4'-dicarboxyamide (N4, N4, N4', N4'-tetrakis (2-hydroxyethyl) biphenyl- under a nitrogen atmosphere After dispersing 4,4'-dicarboxamide (13.0 g, 31.3 mmol) and triethylamine (19.0 g, 187.8 mmol) in dichloromethane (200 mL), the compound trimethylsilyl chloride (13.5 g, 125.2 mmol) was added. Then, the mixture was stirred at 0 ° C. for 2 hours and at room temperature for 16 hours. After completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate (300 ml) was added, and the aqueous solution layer was extracted twice with dichloromethane (200 mL). This was treated with magnesium sulfate (10 g) and dried. The filtered filtrate is concentrated to concentrate N4, N4, N4', N4'-tetrakis (2- (trimethylsilyloxy) ethyl) biphenyl-4,4'-dicarboxamide (N4, N4, N4', N4'-tetracis ( 2- (Trimethylsilyloxy) ethyl) biphenyl-4,4'-dicarboxamide, 17.5 g, yield 79.3%) was produced.
MS[M+H]+=705 MS [M + H] + = 705
製造例2:架橋剤の製造
前記クロロトリメチルシラン(Chlorotrimethylsilane)の代わりにクロロトリエチルシラン(Chlorotriethylsilane)を使用したことを除いて、前記製造例1と同様の方法で、N4,N4,N4',N4'−テトラキス(2−(トリエチルシリルオキシ)エチル)ビフェニル−4,4'−ジカルボキシアミド(N4,N4,N4',N4'−tetrakis(2−(triethylsilyloxy)ethyl)biphenyl−4,4'−dicarboxamide)を製造した。 N4, N4, N4', N4'-tetrakis (2- (triethyl)) in the same manner as in Production Example 1 except that chlorotriethylsilane was used instead of chlorotrimethylsilane. Cyriloxy) ethyl) biphenyl-4,4'-dicarboxyamide (N4, N4, N4', N4'-tetrakis (2- (triethylsilyloxy) ethyl) biphenyl-4,4'-dicarboxamide) was produced.
MS[M+H]+=872 MS [M + H] + = 872
比較製造例1:架橋剤の製造
前記製造例1の反応物であるN4,N4,N4',N4'−テトラキス(2−ヒドロキシエチル)ビフェニル−4,4'−ジカルボキシアミド(N4,N4,N4',N4'−tetrakis(2−hydroxyethyl)biphenyl−4,4'−dicarboxamide)を比較製造例1の架橋剤として使用した。
Comparative Production Example 1: Production of Crosslinking Agent N4, N4, N4', N4'-tetrakis (2-hydroxyethyl) biphenyl-4,4'-dicarboxyamide (N4, N4'), which is the reaction product of Production Example 1. N4', N4'-tetracis (2-hydroxyethyl) biphenyl-4,4'-dicarboxamide) was used as the cross-linking agent of Comparative Production Example 1.
<実施例:感光性組成物および感光材料の製造> <Example: Production of photosensitive composition and photosensitive material>
<実施例> <Example>
実施例1:感光性組成物の製造
下記化学式Aで表されるジアミンDA1 5.0g(13.3mmol)を無水N−メチルピロリドン(NMP)71.27gに完全に溶かした。そして、ice bath下で1,3−ジメチル−シクロブタン−1,2,3,4−テトラカルボン酸二無水物(DMCBDA)2.92g(13.03mmol)を前記溶液に添加し、約16時間常温で攪拌して重合体P−1を製造した。GPCにより前記重合体P−1の分子量を確認した結果、数平均分子量(Mn)が15,500g/molであり、重量平均分子量(Mw)が31,000g/molであった。そして、重合体P−1のモノマー構造は、使用したモノマーの当量比によって決められるもので、分子内のイミド構造の比率が50.5%、アミック酸構造の比率が49.5%であった。
[化学式A]
[Chemical formula A]
下記化学式Bで表されるジアミンDA2 19.743g(0.099mol)を無水N−メチルピロリドン(anhydrous N−methyl pyrrolidone:NMP)225.213gに完全に溶かした。そして、ice bath下でピロメリット酸二無水物(pyromellitic dianhydride、PMDA)20.0g(0.092mol)を前記溶液に添加して、常温で約16時間攪拌して重合体Q−1を製造した。GPCにより前記重合体Q−1の分子量を確認した結果、重量平均分子量(Mw)が27,000g/molであった。
[化学式B]
[Chemical formula B]
前記のように製造した重合体P−1 10gと重合体Q−1 10gをNMP12.4gとn−ブトキシエタノール7.6g(重量比率8:2)を入れ、5wt%溶液を得た。そして、前記溶液に架橋剤として、前記製造例1で得られた架橋剤を全体溶液に対して5重量%添加した後、25℃で16時間攪拌した。得られた溶液をポリ(テトラフルオロエチレン)材質の気孔サイズが0.1μmであるフィルターで加圧ろ過して、感光性組成物を製造した。 10 g of the polymer P-1 and 10 g of the polymer Q-1 produced as described above were added with 12.4 g of NMP and 7.6 g of n-butoxyethanol (weight ratio 8: 2) to obtain a 5 wt% solution. Then, as a cross-linking agent, 5% by weight of the cross-linking agent obtained in Production Example 1 was added to the solution, and then the mixture was stirred at 25 ° C. for 16 hours. The obtained solution was pressure-filtered with a filter having a pore size of a poly (tetrafluoroethylene) material of 0.1 μm to produce a photosensitive composition.
実施例2:感光性組成物の製造
前記製造例1で得られた架橋剤を全体溶液に対して10重量%添加したことを除いて、前記実施例1と同様の方法で、感光性組成物を製造した。
Example 2: Production of Photosensitive Composition The photosensitive composition is prepared in the same manner as in Example 1 except that the cross-linking agent obtained in Production Example 1 is added in an amount of 10% by weight based on the total solution. Manufactured.
実施例3:感光性組成物の製造
前記製造例1で得られた架橋剤の代わりに前記製造例2で得られた架橋剤を添加したことを除いて、前記実施例1と同様の方法で、感光性組成物を製造した。
Example 3: Production of Photosensitive Composition By the same method as in Example 1 except that the cross-linking agent obtained in Production Example 2 was added in place of the cross-linking agent obtained in Production Example 1. , A photosensitive composition was produced.
実施例4:感光性組成物の製造
前記製造例1で得られた架橋剤の代わりに前記製造例2で得られた架橋剤を全体溶液に対して10重量%添加したことを除いて、前記実施例2と同様の方法で、感光性組成物を製造した。
Example 4: Production of Photosensitive Composition The above, except that the cross-linking agent obtained in Production Example 2 was added in an amount of 10% by weight based on the total solution in place of the cross-linking agent obtained in Production Example 1. A photosensitive composition was produced in the same manner as in Example 2.
比較例1:感光性組成物の製造
前記製造例1で得られた架橋剤の代わりに比較製造例1におけるN4,N4,N4',N4'−テトラキス(2−ヒドロキシエチル)ビフェニル−4,4'−ジカルボキシアミド(N4,N4,N4',N4'−tetrakis(2−hydroxyethyl)biphenyl−4,4'−dicarboxamide)を添加したことを除いて、前記実施例1と同様の方法で、感光性組成物を製造した。
Comparative Example 1: Production of photosensitive composition N4, N4, N4', N4'-tetrakis (2-hydroxyethyl) biphenyl-4,4 in Comparative Production Example 1 instead of the cross-linking agent obtained in Production Example 1 Photosensitized in the same manner as in Example 1 above, except that'-dicarboxamide (N4, N4, N4', N4'-tetrakis (2-hydroxhyel) biphenyl-4,4'-dicarboxamide) was added. A sex composition was produced.
前記実施例および比較例の感光性組成物の組成を整理すれば下記表1のとおりである。
<実験例> <Experimental example>
1)貯蔵安定性
前記実施例および比較例で製造した感光性組成物に対して、初期粘度および常温で30日間保管した以降の粘度をそれぞれ測定して、下記数式1によって粘度の変化率を測定した。
1) Storage stability For the photosensitive compositions produced in the above Examples and Comparative Examples, the initial viscosity and the viscosity after storage at room temperature for 30 days were measured, respectively, and the rate of change in viscosity was measured by the following formula 1. did.
前記感光性組成物の粘度は、25℃の温度、0.5rpmの回転速度およびRV−7番スピンドルを用い、ブルックフィールド粘度計で回転力(torque)により測定した。 The viscosity of the photosensitive composition was measured by torque with a Brookfield viscometer using a temperature of 25 ° C., a rotation speed of 0.5 rpm and an RV-7 spindle.
[数式1]
粘度変化率(%)=(常温で30日間保管後の感光性組成物の粘度−初期感光性組成物の粘度)/初期感光性組成物の粘度*100
[Formula 1]
Viscosity change rate (%) = (Viscosity of photosensitive composition after storage at room temperature for 30 days-Viscosity of initial photosensitive composition) / Viscosity of initial photosensitive composition * 100
前記数式1によって求められる粘度の変化率が小さいほど貯蔵安定性に優れていることを意味する。 The smaller the rate of change in viscosity obtained by the above formula 1, the better the storage stability.
2)溶解性
前記実施例および比較例の感光性組成物でそれぞれ使用した架橋剤に対して、上記表1の架橋剤の添加量を満たすように溶媒(γ−ブチロラクトン)に添加した後、10秒間混合した混合溶液を製造して、混合溶液の透明度を肉眼で確認し、以下の基準により溶解性を評価した。
2) Solubility After adding the cross-linking agents used in the photosensitive compositions of the Examples and Comparative Examples to a solvent (γ-butyrolactone) so as to satisfy the addition amount of the cross-linking agent shown in Table 1, 10 A mixed solution mixed for seconds was produced, the transparency of the mixed solution was visually confirmed, and the solubility was evaluated according to the following criteria.
測定結果、混合溶液が透明である場合'優秀'、混合溶液が不透明である場合'不良'と評価し、その結果を下記表2に示す。
上記表2に示すように、実施例1〜4の感光性組成物の場合、製造例1および製造例2で合成した特定構造の架橋剤化合物を使用することによって、感光性組成物の粘度変化率が2.9%以下で優れた貯蔵安定性を示し、かつ優れた溶解性を示すことを確認した。 As shown in Table 2 above, in the case of the photosensitive compositions of Examples 1 to 4, the viscosity of the photosensitive composition is changed by using the cross-linking agent compound having a specific structure synthesized in Production Examples 1 and 2. It was confirmed that when the rate was 2.9% or less, excellent storage stability was exhibited and excellent solubility was exhibited.
反面、比較例1の感光性組成物は、ケイ素含有一価官能基を含まない比較製造例1の架橋剤化合物を使用することによって、前記実施例に比べて貯蔵安定性が非常に不良であるだけでなく、溶解性も不良であることを確認できた。 On the other hand, the photosensitive composition of Comparative Example 1 has very poor storage stability as compared with the above-mentioned Example by using the cross-linking agent compound of Comparative Production Example 1 which does not contain a silicon-containing monovalent functional group. Not only that, it was confirmed that the solubility was also poor.
Claims (14)
[化学式1]
Aは、1価〜4価の芳香族官能基であり、
jは、1〜4の整数であり、
L1およびL2は、それぞれ独立して、炭素数1〜10のアルキレン基または炭素数6〜20のアリーレン基のうちの一つであり、
R1およびR2は、それぞれ独立して、ケイ素含有一価官能基である。 Crosslinking agent compound represented by the following chemical formula 1:
[Chemical formula 1]
A is a monovalent to tetravalent aromatic functional group.
j is an integer of 1 to 4 and
L 1 and L 2 are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
R 1 and R 2 are independent silicon-containing monovalent functional groups.
Aは、下記化学式2で表される2価の芳香族官能基であり、
jは2である、請求項1に記載の架橋剤化合物:
[化学式2]
L3は、単一結合、−O−、−CO−、−S−、−SO2−、−C(CH3)2−、−C(CF3)2−、−COO−、−(CH2)z−、−O(CH2)zO−、−O(CH2)z−、−OCH2−C(CH3)2−CH2O−、−COO−(CH2)z−OCO−、または−OCO−(CH2)z−COO−であり、
zは、それぞれ独立して、1〜10の整数であり、
kは1〜3の整数であり、
nおよびmは、それぞれ独立して、0〜3の整数である。 In the above chemical formula 1,
A is a divalent aromatic functional group represented by the following chemical formula 2.
The cross-linking agent compound according to claim 1, wherein j is 2.
[Chemical formula 2]
L 3 is a single bond, -O-, -CO-, -S-, -SO 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -COO-,-(CH) 2 ) z-, -O (CH 2 ) z O-, -O (CH 2 ) z- , -OCH 2- C (CH 3 ) 2- CH 2 O-, -COO- (CH 2 ) z- OCO -Or -OCO- (CH 2 ) z- COO-,
z is an integer of 1 to 10 independently of each other.
k is an integer from 1 to 3
n and m are independently integers of 0 to 3.
L1およびL2は、それぞれ独立して、炭素数1〜5のアルキレン基である、請求項1または2に記載の架橋剤化合物。 In the above chemical formula 1,
The cross-linking agent compound according to claim 1 or 2, wherein L 1 and L 2 are independently alkylene groups having 1 to 5 carbon atoms.
[化学式1−1]
A'は、2価の芳香族官能基であり、
L4〜L7は、それぞれ独立して、炭素数1〜10のアルキレン基または炭素数6〜20のアリーレン基のうちの一つであり、
R3、R3'、R4、およびR4'は、それぞれ独立して、ケイ素含有一価官能基である。 The cross-linking agent compound according to any one of claims 1 to 3, wherein the cross-linking agent compound represented by the chemical formula 1 includes a compound represented by the following chemical formula 1-1.
[Chemical formula 1-1]
A'is a divalent aromatic functional group,
L 4 to L 7 are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
R 3, R 3 ', R 4, and R 4' are each independently a silicon-containing monovalent functional group.
前記ケイ素含有一価官能基は、下記化学式3で表される官能基である、請求項1から4のいずれか一項に記載の架橋剤化合物:
[化学式3]
R5〜R7は、それぞれ独立して、水素、または炭素数1〜10のアルキル基のうちの一つである。 In the above chemical formula 1,
The cross-linking agent compound according to any one of claims 1 to 4, wherein the silicon-containing monovalent functional group is a functional group represented by the following chemical formula 3.
[Chemical formula 3]
R 5 to R 7 are each independently one of hydrogen or an alkyl group having 1 to 10 carbon atoms.
少なくとも1つ以上のカルボキシル基を含む高分子を含む、感光性組成物:
[化学式1]
Aは、1価〜4価の芳香族官能基であり、
jは、1〜4の整数であり、
L1およびL2は、それぞれ独立して、炭素数1〜10のアルキレン基または炭素数6〜20のアリーレン基のうちの一つであり、
R1およびR2は、それぞれ独立して、ケイ素含有一価官能基である。 A photosensitive composition comprising a cross-linking agent compound represented by the following chemical formula 1; and a polymer containing at least one or more carboxyl groups:
[Chemical formula 1]
A is a monovalent to tetravalent aromatic functional group.
j is an integer of 1 to 4 and
L 1 and L 2 are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
R 1 and R 2 are independent silicon-containing monovalent functional groups.
[化学式4]
A''は、1価〜4価の官能基であり、
aは、1〜4の整数であり、
bは、0〜3の整数であり、
aとbの合計は、1〜4であり、
L8〜L11は、それぞれ独立して、炭素数1〜10のアルキレン基または炭素数6〜20のアリーレン基のうちの一つであり、
R21およびR22のうち少なくとも一つは水素であり、残りはケイ素含有一価官能基であり、
R23およびR24は、それぞれ独立して、ケイ素含有一価官能基である。 The photosensitive composition according to claim 8, further comprising a compound represented by the following chemical formula 4.
[Chemical formula 4]
A'' is a monovalent to tetravalent functional group.
a is an integer of 1 to 4,
b is an integer from 0 to 3 and
The sum of a and b is 1-4,
L 8 to L 11 are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
At least one of R 21 and R 22 is hydrogen and the rest are silicon-containing monovalent functional groups.
R 23 and R 24 are independent silicon-containing monovalent functional groups.
[化学式5]
R5〜R7は、それぞれ独立して、水素、または炭素数1〜10のアルキル基のうちの一つである。 The photosensitive composition according to claim 10, further comprising a compound represented by the following chemical formula 5.
[Chemical formula 5]
R 5 to R 7 are each independently one of hydrogen or an alkyl group having 1 to 10 carbon atoms.
下記化学式6で表される繰り返し単位を含む第1ポリアミック酸(共)重合体、および下記化学式7で表される繰り返し単位を含む第2ポリアミック酸(共)重合体を含む、請求項8から11のいずれか一項に記載の感光性組成物:
[化学式6]
[化学式8]
R13〜R18は、それぞれ独立して、水素または炭素数1〜6のアルキル基であり、
L'は、単一結合、−O−、−CO−、−COO−、−S−、−SO−、−SO2−、−CR19R20−、−(CH2)Z−、−O(CH2)ZO−、−COO(CH2)ZOCO−、−CONH−、またはフェニレンの中から選択されるいずれか一つであり、
R19およびR20は、それぞれ独立して、水素、炭素数1〜10のアルキル基または炭素数1〜10のハロアルキル基であり、
zは1〜10の整数であり、
Y3は、下記化学式9で表される2価の有機基であり、
[化学式9]
Tは、上記化学式8で表される4価の有機基であり、
D1およびD2は、それぞれ独立して、炭素数1〜20のアルキレン基、炭素数1〜10のヘテロアルキレン基、炭素数3〜20のシクロアルキレン基、炭素数6〜20のアリーレン基または炭素数2〜20のヘテロアリーレン基の中から選択されるいずれか一つであり、
Y6は、下記化学式10で表される2価の有機基であり、
[化学式10]
A'は、15族元素であり、
R'は、水素、または炭素数1〜10のアルキルであり、
aは、1〜3の整数であり、
Z1〜Z4のうち少なくとも一つは窒素であり、
残りは炭素である。 The polymer containing at least one or more carboxyl groups is
Claims 8 to 11 include a first polyamic acid (co) polymer containing a repeating unit represented by the following chemical formula 6 and a second polyamic acid (co) polymer containing a repeating unit represented by the following chemical formula 7. The photosensitive composition according to any one of the above:
[Chemical formula 6]
[Chemical formula 8]
R 13 to R 18 are independently hydrogen or alkyl groups having 1 to 6 carbon atoms.
L'is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO 2- , -CR 19 R 20 -,-(CH 2 ) Z- , -O (CH 2) Z O -, - COO (CH 2) Z OCO -, - CONH-, or any one selected from among phenylene,
R 19 and R 20 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, respectively.
z is an integer from 1 to 10.
Y 3 is a divalent organic group represented by the following Chemical Formula 9,
[Chemical formula 9]
T is a tetravalent organic group represented by the above chemical formula 8.
D 1 and D 2 are independently an alkylene group having 1 to 20 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. It is one of the heteroarylene groups having 2 to 20 carbon atoms.
Y 6 is a divalent organic group represented by the following chemical formula 10.
[Chemical formula 10]
A'is a Group 15 element,
R'is hydrogen, or an alkyl having 1 to 10 carbon atoms.
a is an integer from 1 to 3 and
At least one of Z 1 to Z 4 is nitrogen,
The rest is carbon.
[化学式11]
Aは、1価〜4価の芳香族官能基であり、
jは、1〜4の整数であり、
L1およびL2は、それぞれ独立して、炭素数1〜10のアルキレン基または炭素数6〜20のアリーレン基のうちの一つである。 The photosensitive material according to claim 13, wherein the cured product of the photosensitive composition contains a combination of a cross-linking agent compound represented by the following chemical formula 11 and a polymer containing at least one carboxyl group.
[Chemical formula 11]
A is a monovalent to tetravalent aromatic functional group.
j is an integer of 1 to 4 and
L 1 and L 2 are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
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